Halogenated lubricant



I Patented Sept. 2, 1941 UNITED STATES PATENT OFFICE 2,254,337HALOGENATED LUBRICANT William A. Whittier, Kenilworth, m, assignor toThe Pure Oil Company, Chicago, IlL, a'corporation of Ohio No Drawing.Application September 23, 1938.

. Serial No. 231,342

26 Claims.

adding thereto lead soaps, sulfurized hydrocarbons, suliurized fattyoils and phosphorus compounds.

The extent of the improvement accomplished by the various extremepressure additives varies considerably depending upon a number offactors, some of the more important, of which are the particular extremepressure agent used, the quantity'added and the testing method used tomeasure the load carrying capacity. Of these variables, perhaps the mostdifficult to correlate is the load carrying ability as indicated bydifferent testing apparatus. There areCa number of devices commerciallyavailable for determining the extreme pressure characteristics oflubricants, such as the Floyd, Almen, Faville-Levalley, Timken, S. A. E.and a number of others which test E. P. lubricants for more specificapplications. Two of these machines appear to be much more widelyaccepted than any of the others. These are The Timken -Wear andLubricant Tester made by the Timken Roller Bearing Company of Canton,Ohio, and a machine ofiered .as a tentative standard by the Society ofAutomotive Engineers and known as the S. A. E. Extreme Pressure TestingMachine. This machine is made by the Highway Trailer Company ofEdgerton, Wisconsin. Unfortunately there is considerable in the resultsobtained in the two machines and in the application of the results topractical lubricating problems. For example, mineral oil, to which hasbeen added lead soap and active sulfur, will withstand the full load onthe S. A. E. machine, 550 lbs. at 1000 R. P. M., whereas on the Timkenmachine the results are quite low, being of the order of 18 to 25 lbs.beam arm load and a pressure of 10,000- 13,000 lbs. per square inch. I

Lubricating engineers are not entirely in agreement as to just whatthese tests mean in actual performance, although there has been a greatdeal of work done tocorrelat such test results one or the other of thesemachines. It is equally significant that commercially successful E. P.lubricants will not withstand high loads on both the S. A. E. and Timkenmachines, that is, a load of the order of 300 lbs. at 1000 R. P. M. onthe S. A. E. machine and 68 lbs. beam arm load and 25,000 lbs. persquare inch on the Timken machine.

It is an object of, this invention to provide an improved E. P.lubricant.

Another object of this invention is to provide an E. P. lubricant whichwill give superior results in actual service and will givesatisfactorily high results on both the Timken and S. A. E. extremepressure testing machines.

Afurther object of this invention is to provide a stable non-corrosiveE. P. base and lubricantwhich when added to mineral lubricating oilswill be entirely soluble and will impart unusual E. P. characteristicsto the resulting blend without attacking the metal parts with which itcomes in contact. r

Still further objects of this invention will be apparent from thefollowing description.

, I have discovered that certain chlorinated open chain aliphatichydrocarbons, when added to phosphorized or sulfurized and phosphorizedlubricants of the non-corrosive type, for example such as thosedisclosedin application Serial No.

55,200, Whittier et al. and Chittick Patent No. 2,142,998, issuedJanuary10, 1939, produce lubricants which do not hydrolyze, are com pletelysoluble in-mineral oil and show unexpectedly high results on' both theTimken and S. A. E. testing machines. Service tests also showthislubricant to be far. superior to any E. P. lubricant commerciallyavailable. v

The sulfurized-phosphorized lubricant may be prepared in the. followingmanner: v

A homogeneous mixture or 570 pou'ds of Gulf Coast pale oil a SayboltUniversal viscosity of 200 seconds and a pour point of -20 to 25 F. 'and55 pounds of sulfur chloride is prepared in a cold state. This mixtureis added to 9,581 pounds of prime lard oil contained in an enclosedsteam jacketed kettle. The mixture is heated to 275 F. while beingvigorously agitated. At this point the steam is shut off and 814 poundsof flowerso! sulfur are sifted into the contents of the kettle over aperiod'of approximately two willhaverisenirom300to3i4litduringtheflrst 4ties.

three hours indicating that an exothermic reaction was taking place. Thetemperature during the 'Wphour period isnot permitted to drop below320?-to 330 F. and it has been found that it is unnecessary to use anyfurther heat to maintain this temperature after the mixture has beeninitially heated to 300 F. I The sulfurized material is then cooled to atemperature of 220 to 230 F. by circulating the material through coolingcoils and back to the kettle. When this temperature is reached, 44pounds of phosphorous sesqui-sulilde is added slowly over a period of /2hour of continuous a itation. The steam is again turned on at such timesas is necessary to maintain the tempera ture at 220 to 230 F. After theaddition of phosphorus, agitation is continued for a period ofapproximately five hours while the temperature is maintained at 220 to230 F. At the end of this period thercontents of the kettle areimmediately cooled to 130 F. by circulation through the exteriorlylocated cooling coils and pumped tostorage. i

Thephosphorized lubricant maybe made as follows: No. l lard oil isheated with of phosphorous oxychloride at 170 F. to 200 F. for flfteenminutes. During this time only a slight .merous others.

obtained being 0.07%. Halogenated hydrocarbons which have been foundsuitable as extreme .pressure agents according to this invention arehighly halogenated aliphatic compounds which do not boil under about 180C. and which do not substantially hydrolyze at this temperature.Examples of such compounds are hexachlorethane, heptachlorpropane,octachlorbutane, and nu- The matter of boiling point is important fromthe standpoint of the practical application of the lubricant. Lowerboiling compounds may be volatilized and lost at the temperaturesencountered in actual service.

darkening of the-oil occurs. The temperature is slowly increased to 275F. in order to drive off any remaining phosphorous olwchloride. A blacksludge forms in the amount of approximately 25%. 5% of the oil, after ithad been decanted from the sludge, was blended with 95% 0t lubricatingoil. This oil had the following char Halogenated hydrocarbons have beenadded to mineral oil in the past to impart E. P. proper- In general,however, they have not been considered satisfactory due to lack ofstability as shown particularly by the tendency to'hydro-,

r they impart unusual E. P. characteristics to these oils. Those.halogenated open chain hydrocarbons containing at least two carbon atomsand which have all or all but one of the hydrogen replaced by chlorine,have been found to be quite stable'and are very effective E. P. agentswhen used with phosphorized or phosphorized and sulfurized lubricants.'Tetr'achlorbutane, for example, though of sufllciently high boilingpoint (approximately 190 C.) to be satisfactory as an E. P. lubricant isnot. suillciently stable. alcoholic potash will immediately decomposetetrachlorbutane, whereas there is no evidence of a reaction withhexachlorethane under similar conditions. Both of these compounds wereCold 'I'he halogenated compounds may be lubricants themselves or may beused in connection with mineral lubricating oils which already containan extreme pressure base as a phosphorized or a sulfurizedandphosphorized oil base or in connection with the phpsphorized orsulfurized and phosphorized base alone which may be a lubricant initself. pounds when blended in small quantities in mineral lubricatingoil ldo not produce high Timken or S. A. E. tests. However, when theyare added in small quantities to sulfurized-phosphorized lubricantswhich already possess the ability to withstand high loads on the Timkenmachine,

the S. A. E. test of the blend is increased out of all proportion fromwhat would be expected on a basis of tests of the stable halogenatedcompounds in mineral oil. As examples of lubricants within the scope ofthis invention and in order to provide a comparison with existinglubricants,

. the following table has been compiled. All of the boiled in waterforsix hours and the water test-, 7

ed for evidence of hydrolysis ofthe compounds. It wasfound thattetrachlorbutane had hydrolyzed to the extent of 1.14%, whilehexachlorethane showed negligible hydrciysis, the figure lubricantstested were of approximately the same viscosity and were within theviscosity range of S.A.E.90., r

Table I Timken test 'sii a 0a Material Beam at '1000 am Pressure R. P.M. load Pounds Pounda/aq. in. Pounds Mineral oil 12 7, 000 15-50 82%mineral oil 18% suliurlzed and phosphor- 88 36. 600 90 77 19,600 53078.7% mineral oil "tisissfiiiffiiitieriffz. w am 380 4.0% hexachlor78.7% eral oil 5.312; ..Z3?.?.".Z.Z?Pfj. 11 5w m 4.07 he tachlo to e.was. m ineral "063%" -ffiffilfli'fi. 86 3.0% eth x 77.0% mineral oil"teal-3. 5. -fiff ffiiffifi'- a 8% m w 229 ulm lm ii h f" I I s anorfiiintsi o. SEV chIioIrinJIted n-heptane i 68 320 m e o 6% chlorlnatedis'o-octane L"-.. 86 550 335 1 Chlorinated m 04% chlorine by weight. IChlorinated to 03% chlorine by weight.

It will be noted from the above results that mineral oil alone, as mightbe expected, shows very low results on both the Timken and S. A. E.

The stable halogenated com-.-

machines. When 18% of a. sulfurized and phosphorized base is added tothe mineral "oil, the I Timken test is greatly increased, while the S.A. E. test is increased only a small amount. The addition of 4% or 6% ofhexachlorethane to mineral oil increases the pressure as measured by theTimken machine, and as measured by the.

S. A. E. machine only a relatively small amount. It will be noted thatalthough the Timken beam arm load is appreciably increased, the pressureper square inch remains fairly low as calculated from the width of thescar formed on the test block.at thepoint of frictional contact betweenthe test block and cup. With a given beam arm load, the calculatedpressure varies inversely with the width of the scar. However, when 3-5%of hexachlorethane is added to a mineral oil which already contains 18%of a sulfurized and phosphorized base, the Timken test ;remains high,while the S. A. E. test increases v'astly over what would be anticipatedbased on the tests in straight mineral oil. The fact that in some casesthere was a small decrease in the Timken test 1000 to 5000 lbs. persquare inch. The amount of wear on the bronze washer is inverselyrelated to the lubricating quality 'of the lubricant under test. Theresults of these tests are given in Table II.

Table II Hours run Loss of at 5000 lbs. washer metal per sq. m. in gramsMincraloil, S. A.E.90 2 1.028 82% mineral oiL 2 0 18% suli'urized andphosphor 96% mineral oil 2 o no 4% hexachlorethane 1o. mineral"iilfiffififffii.iiifffffi fifiiil v 2 3.0% hcxachlorethanc- 86.4%mineral oil 9.0% sullurized and phosphorized base. 2 0. Oil) 4.0%hexachlorethanc when the chlorine compound was added to thesulfurized-phosphorized lubricant is not considered significant sincethe amount of the decrease is within the accuracy of the machine.- Thatthis unusual increase is not simply due'to the increase in the totalamount of E. P. agents present is evident by the sum of the results onthe blend of mineral oil containing 22% of a 'sulfurized andphosphorized base and on the blend of mineral oil and 4% or 6%hexachlorethane which isv considerably less than the S. A. E. test of.

C] content) or 5% of chlorinated iso-octane (63% Cl content) whenblended with 95% straight mineral oil produced an unusually high S. A.E. test for this class of compounds.

play, as in turning a corner. The thrust machine alternately loads andunloads these washers four times a minute. The load is adjusted at thestart of the test and may be varied from 3000 lbs./sq.'in. load. (Wouldnot hold greater load.)

It isa-pparent from the data in Table II that the combinations ofmineral oil, sulfurized and phosphorized base and hexachlorethane giveconsiderably better results, indicating less wear and superiorlubricating properties, than would be expected from the tests oneither'the sulfurized and ph'osphorized base or hexachlorethane whenblended with'mineral oil. In addition to the wear being less with thepreferred combination of materials, the appearance of the bronze washersFurtained.

Table III St:fl1l;1 H g Timkentest s A E me an exa- Oar Mm-eralphosphochlor- Mileage Backload at rized ethane Beam P 8 base loadressm'e 7 Inches Lila/tam. I Per cent Per cent Per cent 0 0. 006 '38Plymouth 78.7 11.3 4.0 4,100 0.000 86 35,250 ass y g 8 11,500 0.000 38Plymouth 78.7 11.3 4.0 2 670 8888 00 21,250 .150 as Chevrolet 10.5 11.53.0 5 8 8888 as 30,500 340 'as Chrysler Royals--." 10.5 11.5 3.0 8 8% 8038,250 350 ther investigation showed that these. compounds were unstableand for this reason they are un-- washers in the differential assemblyof a rear axle. These washers are located in back of the diiierential orspider gears and receive sudden The maximum wear on any of the indicatedsets of gears is shown by the increase in backlash of 0.0065 obtained onthe Chevrolet. In addition the gears were not scuffed, scratched ordiscolored, thereby further showing'the unusual properties of thislubricant.

Notonly domy lubricants have high E. P. properties and reducewear asshown in the foregoing tables of data, but the corrosion on ferrousmetals ordinarily encountered with various-chlorinated compounds used inmineral lubricating oil as E. P. additives, is substantially, if notentirely eliminated. Comparative tests on samples of ferrous metals weremade by partially and severe loads whenever the gears come intoimmersing small samples of the metals in mineral oil containing 6% ofhexachlorethane at a temperature of approximately 460 F. Similar sampleswere tested in an identical manner using the same mineral oils, blendedwith 6% hexachlorethane and 18% of a sulfurized and phosphorized base.In the former tests the metal pieces were discolored by the presence ofa dark brown layer of material, indicating that the surface of the metalhad been attacked. In the tests where the sulfurized and phosphorizedbase formed 'part of the blend, the metal surfaces after the testremained clean andbright and showed no evidence of any corrosion. It isapparent from these results that the sulfurized and phosphorized basehas an inhibiting action on the corrosive properties at elevatedtemperatures of hexachlorethane in mineral oil. The metal samples usedwere small sections of ferrous sheet stock known as shim stock" and thejournals normally used in the Faville-Levalley lubricant testingmachine.

It is recognized that the temperature selected for the test is wellabove the temperature usually approached by a body of lubricant evenunder conditions of high rubbing loads, but it is also well establishedthat the metal surfaces at the points of frictional contact achievetempera- .tures well above the temperature of the indicated corrosiontests. For this reason the corrosion test results presented are believedto give a good indication of the behavior to be anticipated by E. P.lubricants under actual service conditions.

It is obvious the quantity of halogenated compound used may vary withinrather wide limits although from approximately 1% to 6% is generallypreferred where E. P'. characteristics are important. The upper limit of6% has been mentioned only because with the methods of testing nowavailable it has been found that maximum results can be obtained byadding this amount. There does not appear to be any reason, however, whyquantities in excess of 6% may not be used. The quantity of phosphorizedor sulfurized and phosphorized base preferably varies from approximatelyto 25%, although these proportions are not critical and the inven- WhatI claim is:

' hydrocarbon having a boiling point not subtion contemplates the use ofthesematerlals in furized and phosphorized E. P. base and to use thisbase as a lubricant or to add it to mineral oil and use the resultingmixture as a lubricant, or to bring about any mixture of theaforementioned com nents in any one of a number of ways that will beobvious to those skilled in the art.

It has also been .found that these lubricants containing a phosphorizedor. sulfurined and phosphorlzed base and a stable halogenatedhydrocarbon 'are excellent cutting fluids for ma.-

chine cutting tools as well as grinding and drawing oils. They may 'beusedeither straight or emulsifled with water. The most noticeablecharacteristics of the-- perfo mance of these lubricants as cuttingfluids "the increased life of the cutting edge of the iised and the im-Drovedbrlght, clean-lbolriii onthe ma- .chined' surface. 1 v

1. A lubricant comprising mineral lubricatin oil, a phosphorized fattyoil and a stable highly halogenated aliphatic hydrocarbon having aboiling point not substantially below 180 C.

2. 'A' lubricant comprising mineral lubricating oil, a phosphorized andsulfurized fatty oil and. a stable highly halogenated aliphatichydrocarbon having a boiling point not substantially below 180 C.

3. .A lubricant comprising a phosphorized fatty oil and a stable highlyhalogenated aliphatic stantially below 180" C.

4. A lubricant comprising a phosphorized and 'sulfurized fatty oil and astable highly haloge'nated aliphatic hydrocarbon having a boiling pointnot substantially below 180? C.

5. A lubricant comprising mineral lubricating oil, a phosphonized' fattyoil and a stable highly chlorinated aliphatic hydrocarbon having aboiling point not substantially below 180 C.

6. A lubricantcomprising' mineral lubricating oil, a phosphorized andsulfurized fatty oil and a stable highly chlorinated aliphatichydrocarbon having a boiling point not substantially below 180 C.

' '7. A lubricant comprising a phosphorized fatty oil and a stablehighly chlorinated aliphatic hydrocarbon having a boiling point notsub-- tially below 180 C. and containing not less than chlorine.

9. A lubricant comprising a phosphorized and sulfurized fatty oil and astable highly chlorinated aliphatic hydrocarbon having a boiling pointnot substantially below C.

.5 10. A lubricant comprising a phosphorized and sulfurized fatty oiland a stable highly chlorinated aliphatic hydrocarbon having a boilingpoint not substantially below 180 C. and containing not less than 85%chlorine.

, 11. A lubricant comprising mineral lubricating oil, a phosphorizedfatty oil and a stable highly halogenated aliphatic. hydrocarbon havinga boiling point not substantially below 180 C. and in which all of thehydrogen has been replaced by halogen.

12. A lubricant comprising mineral lubricating oil, a phosphori'zedfatty oil and a stable highly chlorinated aliphatic hydrocarbon having aboiling point not substantially below 180 C. and in which all of thehydrogen has been replaced by chlorine. I v

13. A lubricant comprising mineral lubricating oil, sulfurized andphosphorized fatty oil and I hexachlorethane.

14. A lubricant comprising mineral lubricating oil, suit andphosphorized fatty oil and heptachlorpropane.

15. A lubricant comprising apprordmately 1% to'6% hexachlorethane, 5%to.25% sulfurized and phosphorized fatty oil, and mineral oil.

16. A lubricant comprising approximately 1% to 6%. heptachlorpropane, 5%to 25% sulfurized and phosphorlzed fatty oil, and mineraloil.

17. A lubricant comprising a major portion of mineral lubricating oil,a-minor proportion of phosphorized fatty oil and halogenated'aliphaticlligodrocarbon boiling not substantially below i8. A lubricant inaccordance with claim where the, halogen is chlorine.

19. A lubrlcantcomprising mineral lubricating oil, phosphorlzed fattyp11 and a stable highly halogenated aliphatic hyrocarbon having aboilingpoint not substantially. below 180 C., which hydrocarbon is selectedfrom the group consisting of two to four carbon atom hydrocarbons,

20. A lubricant comprising mineral lubricating oil, phosphorized andsulfurized fatty oil and a stable highly halogenated aliphatichydrocarbon having a boiling point not substantially below 180? C.,which hydrocarbon is selected from the group consisting of two to fourcarbon atom hydrocarbons.

21. A lubricant comprising mineral lubricating oil, sulfurized andphosphorized fatty oil and octachlorbutane.

22. A lubricant comprising mineral lubricating w oil, phosphorized fattyoil and octachlorbutane.

23. Method of lubricating relatively moving metallic surfaces infrictional engagement with each other which comprises bringing incontact and chemically reacting therewith at the point of frictionalengagement a lubricant composition comprising mineral lubricatingbil,phos- 24. Method of lubricating relatively moving metallic surfaces infrictional engagement with each other which comprises bringing incontact and chemically reacting therewith at the point of frictionalengagement a lubricant composition comprising phosphorized andsulfurized fatty oil and stable highly halogenated aliphatichydrometallic surfaces in frictional engagement with phorized fatty oiland a stable highly halogenated aliphatic hydrocarbon having a boilingpoint not substantially below 180? 0.

carbon having a boiling point not substantially below 180 C.

25. Method of lubricating relatively moving fatty oil and mineral oil. a

